EP3455278B1 - Poly-(aryl-ether-ketone) (paek) composition with a low content of volatile compounds and use of same in a sintering method - Google Patents
Poly-(aryl-ether-ketone) (paek) composition with a low content of volatile compounds and use of same in a sintering method Download PDFInfo
- Publication number
- EP3455278B1 EP3455278B1 EP17725705.2A EP17725705A EP3455278B1 EP 3455278 B1 EP3455278 B1 EP 3455278B1 EP 17725705 A EP17725705 A EP 17725705A EP 3455278 B1 EP3455278 B1 EP 3455278B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- ketone
- ether
- weight
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 71
- 238000000034 method Methods 0.000 title claims description 36
- 238000005245 sintering Methods 0.000 title claims description 29
- 150000001875 compounds Chemical class 0.000 title description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 150000008378 aryl ethers Chemical class 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- -1 aromatic acid chlorides Chemical class 0.000 claims description 15
- 230000005670 electromagnetic radiation Effects 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 239000002841 Lewis acid Substances 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 238000000149 argon plasma sintering Methods 0.000 description 6
- 238000007336 electrophilic substitution reaction Methods 0.000 description 6
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000004696 Poly ether ether ketone Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920002530 polyetherether ketone Polymers 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920001643 poly(ether ketone) Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920006260 polyaryletherketone Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000003381 solubilizing effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940082150 encore Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001655 poly(etheretheretherketone) Polymers 0.000 description 2
- 229920001657 poly(etheretherketoneketone) Polymers 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- ITVUPWDTDWMACZ-UHFFFAOYSA-N (4-phenoxyphenyl)-phenylmethanone Chemical compound C=1C=C(OC=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 ITVUPWDTDWMACZ-UHFFFAOYSA-N 0.000 description 1
- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- CSWLPMHPPCPQHC-UHFFFAOYSA-N 1-(benzenesulfonyl)-4-phenoxybenzene Chemical compound C=1C=C(OC=2C=CC=CC=2)C=CC=1S(=O)(=O)C1=CC=CC=C1 CSWLPMHPPCPQHC-UHFFFAOYSA-N 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- FPWNLURCHDRMHC-UHFFFAOYSA-N 4-chlorobiphenyl Chemical group C1=CC(Cl)=CC=C1C1=CC=CC=C1 FPWNLURCHDRMHC-UHFFFAOYSA-N 0.000 description 1
- 101100352919 Caenorhabditis elegans ppm-2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JKFWKYCRXYOPRC-UHFFFAOYSA-N [4-(4-phenoxyphenoxy)phenyl]-phenylmethanone Chemical compound C=1C=C(OC=2C=CC(OC=3C=CC=CC=3)=CC=2)C=CC=1C(=O)C1=CC=CC=C1 JKFWKYCRXYOPRC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
Definitions
- a polyaryletherketone (PAEK) composition for use as a powder in a layer-by-layer additive manufacturing process of a three-dimensional object by sintering said powdered material. by electromagnetic radiation. More particularly, it relates to a poly (aryl-ether-ketone) (PAEK) composition with a low level of volatile compounds.
- the electromagnetic radiation may be infrared radiation or ultraviolet radiation from a laser beam, in the case of laser sintering (still often referred to as "laser sintering" in English terminology), or any other source of radiation.
- laser sintering in the present description includes all these processes regardless of the type of radiation. Although in the following text reference is most often made to the laser sintering method, what is written for this method is of course valid for other sintering processes.
- Poly (aryl ether ketones) are well known high performance technical polymers. They are used for demanding applications in temperature and / or mechanical or chemical stresses. These polymers are found in fields as diverse as aeronautics and space, offshore drilling, automotive, rail, marine, wind, sports, building, electronics and implants. medical. They can be implemented by all thermoplastic processing technologies, such as molding, compression, extrusion, spinning, dusting or sinter prototyping.
- nucleophilic substitution process Two synthetic routes are used to prepare poly-aryl-ether-ketones.
- a first way lies in a so-called nucleophilic substitution process. This process is however complex to implement, access to the monomers being difficult because it is necessary to prepare special fluorinated or chlorinated monomers.
- the synthesis conditions of the nucleophilic substitution process are also difficult (350 ° -400 ° C. in diphenylsulfone) and the post-reaction treatments are restrictive (removal of salts and difficult solvent).
- a second way lies in a so-called electrophilic substitution process, which can be conducted at high temperature as at room temperature.
- the advantage of this second process is the ability to polymerize at a moderate temperature (-20 ° C to 120 ° C) which limits the side reactions.
- monomers such as solvents are more industrially accessible.
- the electrophilic substitution reaction is carried out between one or more aromatic acid chlorides and one or more aromatic ethers in the presence of a Lewis acid. It takes place in a solvent, sometimes in the presence of a dispersant ( US4698393 , WO9500446 ) and is generally carried out in two stages with a first phase at ambient temperature or even below 0 ° C., and then the reaction is completed at a temperature of between 0 ° C. and 120 ° C., depending on the solvent. It is also possible to operate at a higher temperature but this path generates more side reactions. The reaction mixture is then treated with a protic compound which makes it possible to extract all or part of the Lewis acid. The choice of the protic compound is a function of the solvent used.
- the laser sintering process is particularly sensitive to smoke emissions.
- a PAEK powder caused by electromagnetic radiation
- the powder is kept at a high temperature, typically at a temperature above 240 ° C and up to 300 ° C for PEKK, such as marketed by the company Arkema under the reference Kepstan 6000, throughout the duration of construction of the piece, which can last several hours to several tens of hours depending on the complexity of the room.
- the melting of the PAEK powder caused by the electromagnetic radiation emitted by the laser, generates locally and very briefly a temperature peak which can cause the passage of certain components in the vapor phase.
- the set of volatile compounds emitted condenses on the lens of the laser which becomes dirty.
- the energy of the laser beam received by the powder tends to decrease. Therefore, if nothing is done to clean the lens, the mechanical properties of the pieces made by laser sintering decrease over time, because the more the lens gets dirty, the more the energy of the electromagnetic radiation received by the powder decreases, and less sintering is effective.
- PAEK compositions releasing little fumes or condensable vapors, during the construction of three-dimensional parts, are therefore particularly interesting for this sintering application.
- the patent application WO2014013202 filed by the applicant, describes a process for the preparation of poly-aryl-ether-ketone by electrophilic substitution reaction between one or more aromatic acid chlorides and a or a plurality of aromatic ethers in the presence of a Lewis acid.
- This reaction is carried out in an aprotic solvent solubilizing water only very slightly and in two stages.
- a first phase of the reaction is carried out at a temperature between -5 ° C and 25 ° C with stirring, and the reaction is completed at a temperature between 50 and 120 ° C.
- the PAEK obtained then brought into contact with the reaction medium with water in the presence of acid and is separated from the liquid effluents.
- a subsequent step of washing the PAEK obtained with water makes it possible to extract all or part of the Lewis acid.
- the Applicant has found that it is preferable to avoid the use of alcohol to carry out this washing step, because the alcohol contributes to the appearance of side reactions, which make it less stable. This process therefore makes it possible to obtain a very stable polymer.
- the composition of PAEK obtained by this process still generates condensable vapors during sintering, which means that it still contains significant levels of compounds that can pass into the vapor phase under the effect of the radiation. electromagnetic.
- the Applicant has therefore sought to further improve the composition of PAEK, in order to reduce the contents of compounds capable of vaporizing under the action of electromagnetic radiation and to foul the lens of the optical system of the sintering equipment.
- the object of the invention is to provide a poly-aryl-ether-ketone composition comprising aromatic ether and aluminum contents sufficiently low that they no longer generate condensable vapors liable to foul the system lens. optical sintering equipment.
- Another object of the invention is to propose a process for synthesizing a PAEK composition which makes it possible to eliminate sufficiently the compounds that are capable of vaporizing so that they do not generate vapors of a nature to foul the lens of the optical system. sintering equipment.
- the object of the invention is to propose a three-dimensional article obtained by sintering a powder of such a PAEK composition, layer-by-layer, using an electromagnetic radiation, said three-dimensional article having mechanical properties. satisfactory and substantially constant over time.
- the invention relates to a poly (aryl-ether-ketone) (PAEK) composition, suitable for use in a three-dimensional layer-by-layer construction method by sintering caused by electromagnetic radiation, said composition being characterized in that it comprises an aromatic ether content of between 0 and 0.4% by weight and an aluminum mass content of less than 1000 ppm, preferably less than 600 ppm and more preferably less than 500 ppm.
- PAEK poly (aryl-ether-ketone)
- Such a composition does not generate condensable vapors or in an amount sufficiently small not to generate a fouling of the lens, at the time of its sintering.
- the Applicant has surprisingly discovered that the composition of PAEK, when synthesized by a conventional electrophilic substitution reaction, can be washed a first time with a water / alcohol mixture to eliminate aluminum derived from Lewis acid.
- the alcohol is not a solvent sought to perform the washing step because it is known to cause side reactions.
- the alcohol is mixed with water in mass proportions of between 95 and 60%, preferably between 95 and 80%, the mixture makes it possible both to reduce the content of aromatic ethers, but also the content aluminum without leading to side reactions.
- the alcohol is chosen from at least one of the following alcohols: methanol, ethanol or isopropanol.
- the invention further relates to a use of such a powder composition in a layer-by-layer object-forming process by sintering caused by electromagnetic radiation.
- the invention relates to a three-dimensional article obtained by sintering a layer-by-layer powder using electromagnetic radiation, said powder being characterized in that its composition is in accordance with that described above.
- construction temperature refers to the temperature at which the powder bed, of a constituent layer of a three-dimensional object under construction, is heated during the layer-by-layer sintering process of the powder.
- the PAEK composition according to the invention is synthesized from different combinations of aromatic acid di-chlorides and acid monochlorides and aromatic ethers and / or aromatic biphenyls.
- the acid chlorides of terephthaloyl chloride (TCl) and disophthaloyl chloride (ICl) or mixtures thereof will be selected in proportions so that in the final PAEK structure there is a ratio of para-dicetophenyl unit / meta-diketophenyl of 100 to 50% and preferably 85 to 55% and more particularly 82 to 60%.
- the monochlorides of acids will be selected from benzoyl chloride and benzenesulphonyl chloride.
- aromatic ethers or the following aromatic biphenyls are preferably chosen: Diphenyl ether, 1,4- (phenoxybenzoyl) benzene (EKKE), biphenyl, 4-phenoxybenzophenone, 4-chlorobiphenyl, 4- (4- phenoxyphenoxy) benzophenone, and biphenyl 4-benzenesulfonylphenyl phenyl ether.
- At least 50%, preferably at least 70% and more particularly, at least 80% of the X groups are a carbonyl group, and at least 50%, preferably at least 70% and more particularly at least at least 80% of the Y groups represent an oxygen atom.
- 100% of the X groups denote a carbonyl group and 100% of the Y groups represent an oxygen atom.
- the PAEKs used in the invention are chosen from PEKK, PEEK or PEEK-based copolymers, PEK or PEK-based copolymers.
- Lewis acids are preferably used: anhydrous aluminum trichloride, anhydrous aluminum tribromide, and more preferably preferred is anhydrous aluminum trichloride.
- the solvents used are solvents of the acid chlorides and non-solvents of the polymer and solubilizing the water at a content ⁇ 0.2% by mass, preferably ⁇ 0.05% by mass.
- it is orthodichlorobenzene.
- the different phases of the synthesis process can be carried out in the same reactor or a succession of several reactors.
- a first phase of the reaction is carried out at a temperature between -5 ° C and 25 ° C with stirring, and then the polymerization reaction is completed at a temperature between 50 and 120 ° C.
- the PAEK obtained is separated from the liquid effluents after contacting the reaction medium with water in the presence of acid. This separation step is followed by a washing step.
- this washing step consists in bringing the synthesized PAEK, for example a PEKK, into contact with a water / alcohol mixture, with stirring between 15 and 60 ° C., preferably between 25 and 50 ° C., and maintaining this stirring for one hour.
- This washing sequence can be divided into several successive sequences according to the size of the equipment used.
- the water / alcohol mixture used represents from 15 to 50 times the mass of PAEK to be washed.
- the water can be acidified to 10% pure hydrochloric acid, preferably 4%.
- the alcohol is preferably chosen from at least one of the following alcohols: methanol, ethanol or isopropanol. It plays the role of solvent and complexing of aluminum and thus promotes its elimination.
- the proportions of alcohol in the mixture must not be too high so as not to cause the appearance of side reactions. They should not be too weak either to allow sufficient removal of aluminum.
- the mass proportions of alcohol in the water / methanol mixture are preferably between 95 and 60%, preferably between 95 and 80%.
- reaction mixture is separated from the majority of the juices by a suitable separator.
- the juices are subjected to appropriate treatments, decantation, neutralization, distillation and resin treatment to recover or recycle in the process.
- the polymer is then subjected to several additional washing steps with water or acidic water, followed by separation.
- a polymer drying step is carried out at a temperature of 20 ° C higher than the glass transition temperature Tg under 30 mbar.
- the product obtained has an aromatic ether content of between 0 and 0.4% by weight. Preferably this content is between 0 and 0.3% by weight, and more preferably it is between 0 and 0.2% by weight.
- Aromatic ether by means of compounds of molecular weight less than 500g.mol -1, such as EKKE whose molar mass of 470g / mol.
- the mass content of Al in the product obtained is in turn less than 1000 ppm, preferably less than 600 ppm, and more preferably less than 500 ppm.
- Such a composition may be used in the form of a powder in an object construction method using an electromagnetic radiation, in particular a laser radiation, consisting of irradiating the layer-by-layer with the powder, according to a determined route, to locally melt the poly-aryl ether-ketone and obtain the said object.
- an electromagnetic radiation in particular a laser radiation, consisting of irradiating the layer-by-layer with the powder, according to a determined route, to locally melt the poly-aryl ether-ketone and obtain the said object.
- the composition comprises at least polyether-ketone-ketone (PEKK) which represents more than 60% by mass, preferably more than 70% by weight of the composition, including the boundary.
- PEKK polyether-ketone-ketone
- the remaining 30 to 40% by weight may for example consist of other polymers belonging to the PAEK family, and / or fibers, such as carbon fibers, for example glass fibers, and / or by fillers such as mineral fillers, glass beads or carbon blacks, graphites, graphenes, carbon nanotubes.
- the PAEK composition is preferably a polyether-ketone-ketone (PEKK) composition, and the aromatic ether is (1,4-phenoxybenzoyl) benzene (EKKE).
- PEKK polyether-ketone-ketone
- EKKE (1,4-phenoxybenzoyl) benzene
- the composition is in the form of a powder, ready for use in a sintering process caused by electromagnetic radiation, to produce three-dimensional objects layer-by-layer.
- the invention finally relates to a three-dimensional article obtained by sintering a layer-by-layer powder using electromagnetic radiation, said powder being a PAEK powder having a composition in which the aromatic ether content is between 0 and 0.4% by weight.
- the mass content of aluminum in the composition is less than 1000 ppm, preferably less than 600 ppm, and more preferably less than 500 ppm.
- Such a powder does not generate, or very little, vapors, so that the lens of the sintering equipment does not clog and the three-dimensional articles manufactured with such a powder have satisfactory and constant mechanical properties over time .
- the samples are dissolved in a BTF / HFIP mixture in the presence of an internal standard.
- a first product A synthesized and marketed by the company OPM under the reference OxPEKK, comprises a mass content of EKKE, measured by GC, of 1.13%.
- a product B a PEKK marketed by Arkema under the reference Kepstan 6000 and synthesized according to the process described in document WO2014013202 , with washing exclusively with water, comprises a content of EKKE, measured by GC, of 0.45%.
- a third product C a PEKK Kepstan 6000 synthesized according to the same process as for the product B, but whose first washing step is carried out with a water / methanol mixture whose mass proportions of alcohol are between 95 and 60%, preferably between 95 and 80%, comprises an EKKE content, measured by GC, of 0.25% by weight.
- Example 2 Two samples of product B (samples numbered 5 and 6 in Table II below) and four samples of product C (samples numbered 1 to 4 in Table II below) of Example 1 were compared.
- the aluminum mass content of each sample was measured by the method described above.
- Product B corresponding to a PEKK of the prior art, comprises an aluminum content of between 1900 and 2000 ppm according to the samples.
- Product C according to the invention, comprises an aluminum content which varies from 8 ppm, 9 ppm up to 800 ppm depending on the samples.
- Thermogravimetric analyzes were performed with a Netzsch TG209F1 device.
- This device is composed of two main elements: a very sensitive microbalance coupled to a temperature controlled oven.
- the microbalance is capable of detecting a change of 0.1 mg for a maximum capacity of 1.3 g.
- the sample is placed in a platinum cup and the beam maintains the plate in equilibrium via a current proportional to the mass supported.
- the temperature is regulated between 30 ° C and 1000 ° C with temperature rises up to 200 ° C.min -1 .
- a thermocouple near the sample monitors the temperature and regulates the heating power. Calibration was performed with Indium and Zinc with Curie points of 157 ° C and 420 ° C, respectively.
- composition of PAEK according to the invention thus makes it possible to preserve the sintering equipment and to obtain sintered three-dimensional objects with satisfactory mechanical properties that are constant over time.
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Description
L'invention porte sur une composition de poly-aryl-éther-cétone (PAEK) destinée à être utilisée sous forme de poudre dans un procédé de fabrication additive, couche-par-couche, d'objet tridimensionnel, par frittage de ladite poudre provoqué par un rayonnement électromagnétique. Plus particulièrement, elle concerne une composition de Poly(aryl-éther-cétone) (PAEK) à faible taux de composés volatils.Disclosed is a polyaryletherketone (PAEK) composition for use as a powder in a layer-by-layer additive manufacturing process of a three-dimensional object by sintering said powdered material. by electromagnetic radiation. More particularly, it relates to a poly (aryl-ether-ketone) (PAEK) composition with a low level of volatile compounds.
Le rayonnement électromagnétique peut être un rayonnement infrarouge ou un rayonnement ultraviolet issu d'un faisceau laser, dans le cas du frittage laser (encore souvent dénommé « laser sintering » en terminologie anglo-saxonne), ou de toute autre source de rayonnement. Le terme « frittage » dans la présente description inclut tous ces procédés quel que soit le type de rayonnement. Même si, dans le texte qui suit, on fait référence le plus souvent au procédé de frittage laser, ce qui est écrit pour ce procédé est bien entendu valable pour les autres procédés de frittage.The electromagnetic radiation may be infrared radiation or ultraviolet radiation from a laser beam, in the case of laser sintering (still often referred to as "laser sintering" in English terminology), or any other source of radiation. The term "sintering" in the present description includes all these processes regardless of the type of radiation. Although in the following text reference is most often made to the laser sintering method, what is written for this method is of course valid for other sintering processes.
Les Poly(aryl-éther-cétones) sont des polymères techniques hautes performances bien connus. Ils sont utilisés pour des applications contraignantes en température et/ou en contraintes mécaniques, voire chimiques. On retrouve ces polymères dans des domaines aussi variés que l'aéronautique et le spatial, les forages off-shore, l'automobile, le ferroviaire, la marine, l'éolien, le sport, le bâtiment, l'électronique ou encore les implants médicaux. Ils peuvent être mis en œuvre par toutes les technologies de mise en œuvre des thermoplastiques, tels que le moulage, la compression, l'extrusion, le filage, le poudrage ou encore le prototypage par frittage.Poly (aryl ether ketones) are well known high performance technical polymers. They are used for demanding applications in temperature and / or mechanical or chemical stresses. These polymers are found in fields as diverse as aeronautics and space, offshore drilling, automotive, rail, marine, wind, sports, building, electronics and implants. medical. They can be implemented by all thermoplastic processing technologies, such as molding, compression, extrusion, spinning, dusting or sinter prototyping.
Deux voies de synthèse sont utilisées pour préparer les Poly-aryl-éther-cétones. Une première voie réside dans un procédé dit de substitution nucléophile. Ce procédé est toutefois complexe à mettre en œuvre, l'accès aux monomères étant difficile car il faut préparer des monomères fluorés ou chlorés spéciaux. Les conditions de synthèse du procédé de substitution nucléophile sont également difficiles (350°-400°C dans le diphénylsulfone) et les traitements post- réactionnels sont contraignants (élimination des sels et du solvant difficile).Two synthetic routes are used to prepare poly-aryl-ether-ketones. A first way lies in a so-called nucleophilic substitution process. This process is however complex to implement, access to the monomers being difficult because it is necessary to prepare special fluorinated or chlorinated monomers. The synthesis conditions of the nucleophilic substitution process are also difficult (350 ° -400 ° C. in diphenylsulfone) and the post-reaction treatments are restrictive (removal of salts and difficult solvent).
Une deuxième voie réside dans un procédé dit de substitution électrophile, qui peut être conduit à haute température comme à l'ambiante. L'avantage de ce second procédé tient à la possibilité de polymériser à température modérée (-20°C à 120°C) ce qui limite les réactions secondaires. Par ailleurs, les monomères comme les solvants sont plus accessibles industriellement.A second way lies in a so-called electrophilic substitution process, which can be conducted at high temperature as at room temperature. The advantage of this second process is the ability to polymerize at a moderate temperature (-20 ° C to 120 ° C) which limits the side reactions. Moreover, monomers such as solvents are more industrially accessible.
Ce dernier procédé est largement décrit dans la littérature, comme par exemple dans
La réaction de substitution électrophile est réalisée entre un ou plusieurs chlorures d'acide aromatiques et un ou plusieurs éthers aromatiques en présence d'un acide de Lewis. Elle a lieu dans un solvant, en présence parfois d'un dispersant (
Bien que l'invention ne se limite aucunement à ce procédé, seul le procédé préféré de synthèse par réaction de substitution électrophile est décrit dans la suite de la description.Although the invention is not limited to this process, only the preferred electrophilic substitution reaction synthesis method is described in the following description.
Le procédé de frittage laser est particulièrement sensible aux dégagements de fumées. Lors du frittage d'une poudre de PAEK, provoqué par un rayonnement électromagnétique, la poudre est maintenue à haute température, typiquement à une température supérieure à 240°C et qui peut aller jusqu'à 300°C pour du PEKK, tel que celui commercialisé par la société Arkema sous la référence Kepstan 6000, pendant toute la durée de construction de la pièce, qui peut durer plusieurs heures à plusieurs dizaines d'heure selon la complexité de la pièce. La fusion de la poudre de PAEK, provoquée par le rayonnement électromagnétique émis par le laser, engendre localement et très brièvement un pic de température qui peut entrainer le passage de certains constituants en phase vapeur. L'ensemble des composés volatils émis se condense alors sur la lentille du laser qui s'encrasse. Au fur et à mesure de l'encrassement de la lentille, l'énergie du faisceau laser reçue par la poudre a tendance à diminuer. Par conséquent, si rien n'est fait pour nettoyer la lentille, les propriétés mécaniques des pièces fabriquées par frittage laser diminuent au fil du temps, car plus la lentille s'encrasse, plus l'énergie du rayonnement électromagnétique reçu par la poudre diminue, et moins le frittage est efficace.The laser sintering process is particularly sensitive to smoke emissions. When sintering a PAEK powder, caused by electromagnetic radiation, the powder is kept at a high temperature, typically at a temperature above 240 ° C and up to 300 ° C for PEKK, such as marketed by the company Arkema under the reference Kepstan 6000, throughout the duration of construction of the piece, which can last several hours to several tens of hours depending on the complexity of the room. The melting of the PAEK powder, caused by the electromagnetic radiation emitted by the laser, generates locally and very briefly a temperature peak which can cause the passage of certain components in the vapor phase. The set of volatile compounds emitted condenses on the lens of the laser which becomes dirty. As the lens becomes dirty, the energy of the laser beam received by the powder tends to decrease. Therefore, if nothing is done to clean the lens, the mechanical properties of the pieces made by laser sintering decrease over time, because the more the lens gets dirty, the more the energy of the electromagnetic radiation received by the powder decreases, and less sintering is effective.
Il convient donc d'utiliser une composition de PAEK dont la teneur en composés volatils condensables est suffisamment faible pour assurer la constance des propriétés mécaniques des pièces durant l'ensemble des cycles de construction, tout en limitant les opérations de nettoyage de la lentille.It is therefore appropriate to use a composition of PAEK whose condensable volatile compounds content is sufficiently low to ensure the constancy of the mechanical properties of the parts during all the construction cycles, while limiting the cleaning operations of the lens.
Des compositions de PAEK dégageant peu de fumées ou vapeurs condensables, lors de la construction des pièces tridimensionnelles, sont donc particulièrement intéressantes pour cette application de frittage.PAEK compositions releasing little fumes or condensable vapors, during the construction of three-dimensional parts, are therefore particularly interesting for this sintering application.
La demande de brevet
Après analyse de ces vapeurs condensables, il s'avère qu'elles contiennent encore des composés à base d'éther aromatique et des composés provenant de complexes d'hydroxy d'aluminium.After analysis of these condensable vapors, it appears that they still contain aromatic ether compounds and compounds from aluminum hydroxyl complexes.
La demanderesse a donc cherché à améliorer encore la composition de PAEK, afin de réduire les teneurs de composés susceptibles de se vaporiser sous l'action du rayonnement électromagnétique et d'encrasser la lentille du système optique de l'équipement de frittage.The Applicant has therefore sought to further improve the composition of PAEK, in order to reduce the contents of compounds capable of vaporizing under the action of electromagnetic radiation and to foul the lens of the optical system of the sintering equipment.
L'invention a donc pour but de remédier à au moins un des inconvénients de l'art antérieur. En particulier, l'invention a pour but de proposer une composition de poly-aryl-éther-cétone comprenant des teneurs en éther aromatique et en aluminium suffisamment faibles pour qu'ils ne génèrent plus de vapeurs condensables susceptibles d'encrasser la lentille du système optique de l'équipement de frittage.The invention therefore aims to remedy at least one of the disadvantages of the prior art. In particular, the object of the invention is to provide a poly-aryl-ether-ketone composition comprising aromatic ether and aluminum contents sufficiently low that they no longer generate condensable vapors liable to foul the system lens. optical sintering equipment.
L'invention a en outre pour but de proposer un procédé de synthèse d'une composition de PAEK permettant d'éliminer suffisamment les composés susceptibles de se vaporiser pour qu'ils ne génèrent plus de vapeurs de nature à encrasser la lentille du système optique de l'équipement de frittage.Another object of the invention is to propose a process for synthesizing a PAEK composition which makes it possible to eliminate sufficiently the compounds that are capable of vaporizing so that they do not generate vapors of a nature to foul the lens of the optical system. sintering equipment.
L'invention a enfin pour but de proposer un article tridimensionnel obtenu par frittage d'une poudre d'une telle composition de PAEK, couche-par-couche, à l'aide d'un rayonnement électromagnétique, ledit article tridimensionnel présentant des propriétés mécaniques satisfaisantes et sensiblement constantes dans le temps.Finally, the object of the invention is to propose a three-dimensional article obtained by sintering a powder of such a PAEK composition, layer-by-layer, using an electromagnetic radiation, said three-dimensional article having mechanical properties. satisfactory and substantially constant over time.
Pour cela, l'invention porte sur une composition de Poly(aryl-éther-cétone) (PAEK), apte à être utilisée dans un procédé de construction d'objet tridimensionnel couche-par-couche par frittage provoqué par un rayonnement électromagnétique, ladite composition étant caractérisée en ce qu'elle comprend une teneur en éther aromatique comprise entre 0 et 0,4% massique et une teneur massique en aluminium inférieure à 1000ppm, de préférence inférieure à 600ppm et de manière davantage préférée inférieure à 500ppm.For this purpose, the invention relates to a poly (aryl-ether-ketone) (PAEK) composition, suitable for use in a three-dimensional layer-by-layer construction method by sintering caused by electromagnetic radiation, said composition being characterized in that it comprises an aromatic ether content of between 0 and 0.4% by weight and an aluminum mass content of less than 1000 ppm, preferably less than 600 ppm and more preferably less than 500 ppm.
Une telle composition ne génère pas de vapeurs condensables ou en quantité suffisamment faible pour ne pas générer un encrassement de la lentille, au moment de son frittage.Such a composition does not generate condensable vapors or in an amount sufficiently small not to generate a fouling of the lens, at the time of its sintering.
Selon d'autres caractéristiques optionnelles de la composition :
- de préférence, la teneur en éther aromatique est comprise entre 0 et 0,3% massique,
- de manière davantage préférée, la teneur en éther aromatique est comprise entre 0 et 0,2% massique et encore préféré entre 0 et 0,1% massique,
- la composition comprend en outre une teneur massique en aluminium inférieure à 1000ppm, de préférence inférieure à 600ppm et de manière davantage préférée inférieure à 500ppm et tout particulièrement entre 10 et 250 ppm, voire entre 5 et 100 ppm,
- la composition comprend au moins du polyéther-cétone-cétone (PEKK) qui représente plus de 60% massique, de préférence plus de 70% massique de la composition, borne comprise,
- la composition est une composition de Polyéther-cétone-cétone (PEKK),
- l'éther aromatique est le (1,4-phénoxybenzoyl) benzène,
- la composition se présente sous forme de poudre.
- preferably, the content of aromatic ether is between 0 and 0.3% by weight,
- more preferably, the content of aromatic ether is between 0 and 0.2% by weight and more preferably between 0 and 0.1% by weight,
- the composition further comprises a mass content of aluminum of less than 1000 ppm, preferably less than 600 ppm, and more preferably less than 500 ppm and most preferably between 10 and 250 ppm, or even between 5 and 100 ppm,
- the composition comprises at least polyether-ketone-ketone (PEKK) which represents more than 60% by weight, preferably more than 70% by weight of the composition, including the terminal,
- the composition is a polyether-ketone-ketone (PEKK) composition,
- the aromatic ether is (1,4-phenoxybenzoyl) benzene,
- the composition is in powder form.
Pour obtenir une telle composition, la demanderesse a découvert, de manière surprenante, que la composition de PAEK, lorsqu'elle est synthétisée par une réaction de substitution électrophile classique, pouvait être lavée une première fois avec un mélange eau/alcool afin d'éliminer l'aluminium issu de l'acide de Lewis.To obtain such a composition, the Applicant has surprisingly discovered that the composition of PAEK, when synthesized by a conventional electrophilic substitution reaction, can be washed a first time with a water / alcohol mixture to eliminate aluminum derived from Lewis acid.
Plus particulièrement le procédé de synthèse de la composition consiste à mettre en contact un ou plusieurs chlorures d'acide aromatiques et un ou plusieurs éthers aromatique en présence d'un acide de Lewis dans un solvant ne solubilisant l'eau qu'à une teneur inférieure à 0,05% massique à 25°C à une température comprise entre -5 et +25°C sous agitation, à achever la polymérisation à une température comprise entre 50 et 120°C, puis à mettre en contact le mélange réactionnel avec de l'eau sous agitation en présence éventuelle d'acide, à séparer le poly-aryl-éther-cétone des effluents liquides, à laver le poly-aryl-éther-cétone en présence ou non d'acide et séparer les jus, et enfin à sécher le poly-aryl-éther-cétone obtenu à une température supérieure à la température de transition vitreuse Tg de 20°C ; et ce procédé est plus particulièrement caractérisé en ce que l'étape de lavage du poly-aryl-éther-cétone et de séparation des jus consiste à :
- effectuer un premier lavage à l'aide d'un mélange eau/alcool et séparer les jus,
- effectuer au moins un autre lavage complémentaire avec de l'eau ou de l'eau acide et séparer les jus.
- perform a first wash with a water / alcohol mixture and separate the juices,
- perform at least one additional wash with water or acidic water and separate the juices.
Ainsi qu'il a été expliqué dans le document
L'invention porte en outre sur une utilisation d'une telle composition sous forme de poudre dans un procédé de construction d'objet couche-par-couche par frittage provoqué par un rayonnement électromagnétique.The invention further relates to a use of such a powder composition in a layer-by-layer object-forming process by sintering caused by electromagnetic radiation.
L'invention porte enfin sur un article tridimensionnel obtenu par frittage d'une poudre couche-par-couche à l'aide d'un rayonnement électromagnétique, ladite poudre étant caractérisée en ce que sa composition est conforme à celle décrite ci-dessus.Finally, the invention relates to a three-dimensional article obtained by sintering a layer-by-layer powder using electromagnetic radiation, said powder being characterized in that its composition is in accordance with that described above.
D'autres avantages et caractéristiques de l'invention apparaitront à la lecture de la description suivante donnée à titre d'exemple illustratif et non limitatif.Other advantages and characteristics of the invention will appear on reading the following description given by way of illustrative and non-limiting example.
En préambule, il est précisé que les expressions « compris(e) entre » et/ou « inférieur(e) à » et/ou « supérieur(e) à » utilisées dans le cadre de cette description doivent s'entendre comme incluant les bornes citées.In the preamble, it is clarified that the expressions "included between" and / or "less than" and / or "greater than" used in the context of this description must be understood to include quoted terminals.
Le terme « température de construction » désigne la température à laquelle le lit de poudre, d'une couche constitutive d'un objet tridimensionnel en construction, est chauffé pendant le procédé de frittage couche-par-couche de la poudre.The term "construction temperature" refers to the temperature at which the powder bed, of a constituent layer of a three-dimensional object under construction, is heated during the layer-by-layer sintering process of the powder.
La composition de PAEK selon l'invention est synthétisée à partir de différentes combinaisons de di-chlorures d'acides aromatiques et de monochlorures d'acide et d'éthers aromatiques et/ou de biphényls aromatiques.The PAEK composition according to the invention is synthesized from different combinations of aromatic acid di-chlorides and acid monochlorides and aromatic ethers and / or aromatic biphenyls.
De préférence on choisira les chlorures d'acide parmi le chlorure de téréphthaloyle (TCl) et le chlorure disophthaloyle (ICl) ou leur mélange, dans des proportions pour que dans la structure PAEK finale, il y ait un ratio de motif para-dicetophényle / meta-dicetophényle de 100 à 50% et de préférence de 85 à 55%% et plus particulièrement de 82 à 60%.Preferably, the acid chlorides of terephthaloyl chloride (TCl) and disophthaloyl chloride (ICl) or mixtures thereof will be selected in proportions so that in the final PAEK structure there is a ratio of para-dicetophenyl unit / meta-diketophenyl of 100 to 50% and preferably 85 to 55% and more particularly 82 to 60%.
Les monochlorures d'acides seront choisis parmi le chlorure de benzoyle et le chlorure de benzène sulfonyle.The monochlorides of acids will be selected from benzoyl chloride and benzenesulphonyl chloride.
De préférence on choisira les éthers aromatiques ou les biphényls aromatiques suivants: Le diphényle-éther, le 1,4-(phénoxybenzoyle) benzène (EKKE), le biphényle, le 4-phenoxybenzophénone, le 4-chlorobiphényle, le 4-(4-phénoxyphénoxy) benzophénone, et le biphényl 4-benzènesulphonylphényl phényléther.The aromatic ethers or the following aromatic biphenyls are preferably chosen: Diphenyl ether, 1,4- (phenoxybenzoyl) benzene (EKKE), biphenyl, 4-phenoxybenzophenone, 4-chlorobiphenyl, 4- (4- phenoxyphenoxy) benzophenone, and biphenyl 4-benzenesulfonylphenyl phenyl ether.
Les poly-(aryl-éther-cétones) (PAEK) comportent les motifs de formules suivantes:
(-Ar-X-) et (-Ar1-Y-)
dans lesquelles :
- Ar et Ar1 désignent chacun un radical aromatique divalent;
- Ar et Ar1 peuvent être choisis, de préférence, parmi le 1,3-phénylène, 1,4-phénylène, le 4,4'-biphénylène, le 1,4- naphthylène, le 1,5-naphthylène et le 2,6-naphthylène ;
- X désigne un groupe électroattracteur ; il peut être choisi, de préférence, parmi le groupe carbonyle et le groupe sulfonyle,
- Y désigne un groupe choisi parmi un atome d'oxygène, un atome de soufre, un groupe alkylène, tel que -CH2- et isopropylidène.
(-Ar-X-) and (-Ar 1 -Y-)
in which :
- Ar and Ar 1 each denote a divalent aromatic radical;
- Ar and Ar 1 may be chosen, preferably, from 1,3-phenylene, 1,4-phenylene, 4,4'-biphenylene, 1,4-naphthylene, 1,5-naphthylene and 2, 6-naphthylene;
- X denotes an electron-withdrawing group; it can be chosen, preferably, from the carbonyl group and the sulphonyl group,
- Y denotes a group selected from an oxygen atom, a sulfur atom, an alkylene group, such as -CH 2 - and isopropylidene.
Dans ces motifs X et Y, au moins 50%, de préférence au moins 70% et plus particulièrement, au moins 80% des groupes X sont un groupe carbonyle, et au moins 50%, de préférence au moins 70% et plus particulièrement au moins 80% des groupes Y représentent un atome d'oxygène. Selon un mode de réalisation préféré, 100% des groupes X désignent un groupe carbonyle et 100% des groupes Y représentent un atome d'oxygène.In these units X and Y, at least 50%, preferably at least 70% and more particularly, at least 80% of the X groups are a carbonyl group, and at least 50%, preferably at least 70% and more particularly at least at least 80% of the Y groups represent an oxygen atom. According to a mode of In a preferred embodiment, 100% of the X groups denote a carbonyl group and 100% of the Y groups represent an oxygen atom.
Plus préférentiellement, le poly-arylène-éther-cétone (PAEK) peut être choisi parmi :
- un poly-éther-cétone-cétone, également nommé PEKK, comprenant des motifs de formule I A, de formule I B et leur mélange :
- un poly-éther-éther-cétone, également nommé PEEK, comprenant des motifs de formule II:
Les enchainements peuvent être totalement para (Formule II). De la même façon on peut introduire, partiellement ou totalement, des enchaînements méta dans ces structures au niveau des éthers et des cétones selon les deux exemples des formules III et IV ci-dessous :
Ou encore :
Ou des enchainements en ortho selon la formule V : - un poly-éther-cétone, également nommé PEK, comprenant des motifs de formule VI :
De la même façon, l'enchainement peut être totalement para mais on peut introduire aussi des enchaînements méta partiellement ou totalement (formules VII et VIII):
Ou - un poly-éther-éther-cétone-cétone, également nommé PEEKK, comprenant des motifs de formules IX :
De la même façon on peut introduire des enchaînements méta dans ces structures au niveau des éthers et des cétones. - un poly-éther-éther-éther-cétone, également nommé PEEEK, comprenant des motifs de formules X :
- a poly-ether-ketone-ketone, also called PEKK, comprising units of formula IA, of formula IB and their mixture:
- a poly-ether-ether-ketone, also called PEEK, comprising units of formula II:
Chains can be totally para (Formula II). In the same way, it is possible to introduce, partially or totally, meta sequences in these structures at the level of the ethers and the ketones according to the two examples of the formulas III and IV below:
Or :
Or sequences in ortho according to the formula V: - a poly-ether-ketone, also called PEK, comprising units of formula VI:
In the same way, the sequence can be totally para but one can also introduce meta links partially or totally (formulas VII and VIII):
Or - a poly-ether-ether-ketone-ketone, also called PEEKK, comprising units of formulas IX:
In the same way we can introduce meta sequences in these structures at the level of ethers and ketones. - a poly-ether-ether-ether-ketone, also called PEEEK, comprising units of formulas X:
De la même façon on peut introduire des enchaînements méta dans ces structures au niveau des éthers et des cétones mais aussi des enchaînements biphénols selon la formule XI :
D'autres arrangements du groupe carbonyle et de l'atome d'oxygène sont également possibles.Other arrangements of the carbonyl group and the oxygen atom are also possible.
De préférence, les PAEK utilisés dans l'invention sont choisis parmi les PEKK, le PEEK ou les copolymères à base de PEEK, le PEK ou les copolymères à base de PEK.Preferably, the PAEKs used in the invention are chosen from PEKK, PEEK or PEEK-based copolymers, PEK or PEK-based copolymers.
Lors de la synthèse de ces Poly-aryl-éther-cétones, par le procédé préféré de réaction de substitution électrophile, on utilise de préférence les acides de Lewis suivant : Trichlorure d'aluminium anhydre, tribromure d'aluminium anhydre, et de manière plus préférée le trichlorure d'aluminium anhydre.When synthesizing these polyaryletherketones by the preferred method of electrophilic substitution reaction, the following Lewis acids are preferably used: anhydrous aluminum trichloride, anhydrous aluminum tribromide, and more preferably preferred is anhydrous aluminum trichloride.
Les solvants utilisés sont solvants des chlorures d'acide et non solvants du polymère et solubilisant l'eau à une teneur < 0.2% massique, de préférence <0.05% massique. De préférence, il s'agit d'orthodichloro-benzène.The solvents used are solvents of the acid chlorides and non-solvents of the polymer and solubilizing the water at a content <0.2% by mass, preferably <0.05% by mass. Preferably, it is orthodichlorobenzene.
Les différentes phases du procédé de synthèse peuvent être opérées dans un même réacteur ou une succession de plusieurs réacteurs. Une première phase de la réaction est réalisée à une température entre -5°C et 25°C sous agitation, puis la réaction de polymérisation est achevée à une température comprise entre 50 et 120°C. Le PAEK obtenu est séparé des effluents liquides après mise en contact du milieu réactionnel avec de l'eau en présence éventuelle d'acide. Cette étape de séparation est suivie d'une étape de lavage.The different phases of the synthesis process can be carried out in the same reactor or a succession of several reactors. A first phase of the reaction is carried out at a temperature between -5 ° C and 25 ° C with stirring, and then the polymerization reaction is completed at a temperature between 50 and 120 ° C. The PAEK obtained is separated from the liquid effluents after contacting the reaction medium with water in the presence of acid. This separation step is followed by a washing step.
De manière avantageuse, cette étape de lavage consiste à mettre en contact le PAEK synthétisé, par exemple un PEKK, avec un mélange eau/alcool, sous agitation entre 15 et 60°C, de préférence entre 25 et 50 °C et à maintenir cette agitation pendant une heure. Selon une variante, on peut aussi additionner le mélange eau/alcool dans un réacteur après y avoir introduit le PAEK.Advantageously, this washing step consists in bringing the synthesized PAEK, for example a PEKK, into contact with a water / alcohol mixture, with stirring between 15 and 60 ° C., preferably between 25 and 50 ° C., and maintaining this stirring for one hour. According to one variant, it is also possible to add the water / alcohol mixture to a reactor after having introduced the PAEK therein.
Cette séquence de lavage peut être divisée en plusieurs séquences successives selon la taille de l'équipement utilisé.This washing sequence can be divided into several successive sequences according to the size of the equipment used.
Le mélange eau/alcool utilisé représente de 15 à 50 fois la masse de PAEK à laver. L'eau peut être acidifiée jusqu'à 10% d'acide chlorhydrique pur, de préférence 4%.The water / alcohol mixture used represents from 15 to 50 times the mass of PAEK to be washed. The water can be acidified to 10% pure hydrochloric acid, preferably 4%.
L'alcool est de préférence choisi parmi l'un au moins des alcools suivants : le méthanol, l'éthanol ou l'isopropanol. Il joue le rôle de solvant et de complexant de l'aluminium et favorise ainsi son élimination.The alcohol is preferably chosen from at least one of the following alcohols: methanol, ethanol or isopropanol. It plays the role of solvent and complexing of aluminum and thus promotes its elimination.
Les proportions d'alcool dans le mélange ne doivent cependant pas être trop élevées de manière à ne pas entrainer l'apparition de réactions secondaires. Elles ne doivent pas être trop faibles non plus pour permettre une élimination suffisante de l'aluminium.The proportions of alcohol in the mixture must not be too high so as not to cause the appearance of side reactions. They should not be too weak either to allow sufficient removal of aluminum.
Un compromis doit donc être réalisé sur les proportions en alcool. Ainsi, les proportions massiques d'alcool dans le mélange eau/méthanol sont de préférence comprises entre 95 et 60%, de préférence entre 95 et 80%.A compromise must therefore be made on the proportions of alcohol. Thus, the mass proportions of alcohol in the water / methanol mixture are preferably between 95 and 60%, preferably between 95 and 80%.
Après ce lavage, le mélange réactionnel est séparé de la majorité des jus par un séparateur adapté.After this washing, the reaction mixture is separated from the majority of the juices by a suitable separator.
Les jus sont soumis à des traitements adaptés, décantation, neutralisation, distillation et traitement sur résine permettant de les valoriser ou les recycler dans le procédé.The juices are subjected to appropriate treatments, decantation, neutralization, distillation and resin treatment to recover or recycle in the process.
Le polymère est ensuite soumis à plusieurs étapes de lavage complémentaire avec de l'eau ou de l'eau acide, puis séparation.The polymer is then subjected to several additional washing steps with water or acidic water, followed by separation.
Enfin une étape de séchage du polymère est effectuée à une température supérieure de 20°C à la température de transition vitreuse Tg sous 30 mbar.Finally a polymer drying step is carried out at a temperature of 20 ° C higher than the glass transition temperature Tg under 30 mbar.
Le produit obtenu présente une teneur en éther aromatique comprise entre 0 et 0,4% massique. De préférence cette teneur est comprise entre 0 et 0,3% massique, et de manière davantage préférée elle est comprise entre 0 et 0,2% massique. On entend par éther aromatique des composés de masse molaire inférieure à 500g.mol-1, tel que l'EKKE dont la masse molaire est de 470g/mol. La teneur massique en Al dans le produit obtenu est quant à elle inférieure à 1000ppm, de préférence inférieure à 600ppm, et de manière davantage préférée inférieure à 500ppm.The product obtained has an aromatic ether content of between 0 and 0.4% by weight. Preferably this content is between 0 and 0.3% by weight, and more preferably it is between 0 and 0.2% by weight. Aromatic ether by means of compounds of molecular weight less than 500g.mol -1, such as EKKE whose molar mass of 470g / mol. The mass content of Al in the product obtained is in turn less than 1000 ppm, preferably less than 600 ppm, and more preferably less than 500 ppm.
Une telle composition peut être utilisée sous forme de poudre dans un procédé de construction d'objet à l'aide d'un rayonnement électromagnétique, notamment laser, consistant à irradier couche-par-couche la poudre, selon un tracé déterminé, afin de fondre localement le poly-aryl éther -cétone et obtenir le dit objet.Such a composition may be used in the form of a powder in an object construction method using an electromagnetic radiation, in particular a laser radiation, consisting of irradiating the layer-by-layer with the powder, according to a determined route, to locally melt the poly-aryl ether-ketone and obtain the said object.
La composition comprend au moins du polyéther-cétone-cétone (PEKK) qui représente plus de 60% massique, de préférence plus de 70% massique de la composition, borne comprise. Les 30 à 40 % massiques restants peuvent par exemple être constitués soit par d'autres polymères appartenant à la famille des PAEK, et/ou par des fibres, telles que des fibres de carbone, des fibres de verre par exemple, et/ou par des charges telles que des charges minérales, des billes de verre ou encore par des noirs de carbone, des graphites, des graphènes, des nanotubes de carbone.The composition comprises at least polyether-ketone-ketone (PEKK) which represents more than 60% by mass, preferably more than 70% by weight of the composition, including the boundary. The remaining 30 to 40% by weight may for example consist of other polymers belonging to the PAEK family, and / or fibers, such as carbon fibers, for example glass fibers, and / or by fillers such as mineral fillers, glass beads or carbon blacks, graphites, graphenes, carbon nanotubes.
La composition de PAEK est de préférence une composition de Polyéther-cétone-cétone (PEKK), et l'éther aromatique est le (1,4-phénoxybenzoyl) benzène (EKKE).The PAEK composition is preferably a polyether-ketone-ketone (PEKK) composition, and the aromatic ether is (1,4-phenoxybenzoyl) benzene (EKKE).
La composition se présente sous forme de poudre, prête à être utilisée dans un procédé de frittage provoqué par rayonnement électromagnétique, pour réaliser des objets tridimensionnels couche-par-couche.The composition is in the form of a powder, ready for use in a sintering process caused by electromagnetic radiation, to produce three-dimensional objects layer-by-layer.
L'invention se rapporte enfin à un article tridimensionnel obtenu par frittage d'une poudre couche-par-couche à l'aide d'un rayonnement électromagnétique, ladite poudre étant une poudre de PAEK présentant une composition dans laquelle la teneur en éther aromatique est comprise entre 0 et 0,4 % massique. En outre, la teneur massique en aluminium dans la composition est inférieure à 1000ppm, de préférence inférieure à 600ppm, et de manière davantage préférée inférieure à 500ppm. Une telle poudre ne génère pas, ou très peu, de vapeurs, si bien que la lentille de l'équipement de frittage ne s'encrasse pas et les articles tridimensionnels fabriqués avec une telle poudre présentent des propriétés mécaniques satisfaisantes et constantes au cours du temps.The invention finally relates to a three-dimensional article obtained by sintering a layer-by-layer powder using electromagnetic radiation, said powder being a PAEK powder having a composition in which the aromatic ether content is between 0 and 0.4% by weight. In addition, the mass content of aluminum in the composition is less than 1000 ppm, preferably less than 600 ppm, and more preferably less than 500 ppm. Such a powder does not generate, or very little, vapors, so that the lens of the sintering equipment does not clog and the three-dimensional articles manufactured with such a powder have satisfactory and constant mechanical properties over time .
Les échantillons sont mis en solution dans un mélange BTF/HFIP en présence d'un standard interne.The samples are dissolved in a BTF / HFIP mixture in the presence of an internal standard.
Toutes les analyses ont été réalisées sur un GC VARIAN® 3800 équipé d'un injecteur on-column 1041 et d'un détecteur FID.
- Colonne: MXT 500 Sim Dist 6m / 320µm / ef=0,15µm
- Température Det (FID) =400°C
- Température Injecteur 1041 = régulé à T ≤ 40°C
- Débit colonne (constant flow) = 3ml/min,
- Programmation four = 40°C (2min) → 150°C à 8°C/min
- 150°C (0min) → 330°C(Omin) à 15°C/min
- 330°C (0min) → 360°C(5min) à 25°C/min
- Gaz vecteur = hélium
- Mode d'injection : dans la colonne avec le point d'injection situé dans la partie régulé par le four
- Volume injecté=0,5µl
- Column: MXT 500 Sim Dist 6m / 320μm / ef = 0.15μm
- Det (FID) temperature = 400 ° C
- Injector temperature 1041 = regulated at T ≤ 40 ° C
- Constant flow rate = 3ml / min,
- Oven programming = 40 ° C (2min) → 150 ° C to 8 ° C / min
- 150 ° C (0min) → 330 ° C (Omin) at 15 ° C / min
- 330 ° C (0min) → 360 ° C (5min) at 25 ° C / min
- Vector gas = helium
- Injection mode: in the column with the injection point located in the part regulated by the oven
- Injected volume = 0.5μl
Des essais de frittage ont été réalisés sur trois échantillons de PEKK. Un premier produit A, synthétisé et commercialisé par la société OPM sous la référence OxPEKK, comprend une teneur massique en EKKE, mesurée par GC, de 1,13%. Un produit B, un PEKK commercialisé par la société Arkema sous la référence Kepstan 6000 et synthétisé selon le procédé décrit dans le document
Ces essais de frittage ont été menés à une température de construction de 285°C. Ces essais ont révélés que les deux premiers produits A et B génèrent un dégagement de vapeurs important lors du test (voir tableau I ci-dessous). Ces vapeurs se retrouvent condensées sur la lentille. L'analyse d'un prélèvement de ce condensat montre la présence d'EKKE. En plus d'un encrassement de la machine, ce dépôt sur la lentille modifie l'énergie reçue par la poudre de PEKK qui ne se fritte pas correctement et l'objet tridimensionnel résultant présente alors des propriétés mécaniques qui diminuent avec le temps.
- Peser 0.5g de l'échantillon dans un digitube.Weigh 0.5g of the sample into a digitube.
- Ajouter 10 mL d'acide nitrique 67%Add 10 mL of 67% nitric acid
- Chauffer 2 heures à 99°C dans un bloc chauffantHeat for 2 hours at 99 ° C in a heating block
- Filtrer sur filtre Whatman (589/1 diam 125mm)Filter on Whatman filter (589/1 diam 125mm)
- Compléter au trait de jauge avec un volume final de 25 mL avec de l'eau Milly QMake up to the mark with a final volume of 25 mL with Milly Q water
- Par la technique ICP/AES optique (ICP Vista Pro) VarianBy optical ICP / AES technique (ICP Vista Pro) Varian
- Etalon passé avant et après échantillon pour contrôle de dériveStandard passed before and after sample for drift control
- Longueur d'onde de travail : 396.15 nm pour l'élément aluminiumWorking wavelength: 396.15 nm for the aluminum element
Deux échantillons de produit B (échantillons numérotés 5 et 6 dans le tableau II ci-dessous) et quatre échantillons de produit C (échantillons numérotés 1 à 4 dans le tableau II ci-dessous) de l'exemple 1 ont été comparés. La teneur massique en aluminium de chaque échantillon a été mesurée par la méthode décrite ci-dessus. Le produit B, correspondant à un PEKK de l'art antérieur, comprend une teneur en aluminium comprise entre 1900 et 2000ppm selon les échantillons. Le produit C, conforme à l'invention, comprend une teneur en aluminium qui varie de 8 ppm, 9 ppm jusqu'à 800 ppm selon les échantillons.Two samples of product B (samples numbered 5 and 6 in Table II below) and four samples of product C (samples numbered 1 to 4 in Table II below) of Example 1 were compared. The aluminum mass content of each sample was measured by the method described above. Product B, corresponding to a PEKK of the prior art, comprises an aluminum content of between 1900 and 2000 ppm according to the samples. Product C, according to the invention, comprises an aluminum content which varies from 8 ppm, 9 ppm up to 800 ppm depending on the samples.
Des analyses thermogravimétriques (ATG) ont été réalisées avec un appareil Netzsch TG209F1. Cet appareil est composé de deux éléments principaux: une microbalance très sensible couplée à un four régulé en température. La microbalance est capable de détecter une variation de 0,1 mg pour une capacité maximale de 1,3 g. L'échantillon est placé dans une coupelle en platine et le fléau maintient le plateau en équilibre via un courant proportionnel à la masse supportée. La température est régulée entre 30 °C et 1000 °C avec des montées en température jusqu'à 200 °C.min-1. Un thermocouple à proximité de l'échantillon assure un suivi de la température et régule la puissance de chauffage. L'étalonnage a été effectué avec de l'Indium et du Zinc dont les points de Curie sont respectivement de 157 °C et 420 °C.Thermogravimetric analyzes (ATG) were performed with a Netzsch TG209F1 device. This device is composed of two main elements: a very sensitive microbalance coupled to a temperature controlled oven. The microbalance is capable of detecting a change of 0.1 mg for a maximum capacity of 1.3 g. The sample is placed in a platinum cup and the beam maintains the plate in equilibrium via a current proportional to the mass supported. The temperature is regulated between 30 ° C and 1000 ° C with temperature rises up to 200 ° C.min -1 . A thermocouple near the sample monitors the temperature and regulates the heating power. Calibration was performed with Indium and Zinc with Curie points of 157 ° C and 420 ° C, respectively.
Toutes les analyses ATG sur les échantillons ont été réalisées en isotherme, sous azote, à une température de 285°C, correspondant à la température de construction en frittage laser, pendant une heure. Les pertes de masses mesurées sont indiquées dans le tableau II ci-dessous.
Ces mesures de perte de masse par ATG démontrent qu'il existe une corrélation entre la stabilité thermique de l'échantillon de PEKK et sa teneur en Aluminium. Ainsi, à des teneurs en aluminium inférieures à 1000ppm, la composition de PEKK est stable thermiquement.These ATG mass loss measurements demonstrate that there is a correlation between the thermal stability of the PEKK sample and its aluminum content. Thus, at aluminum contents below 1000 ppm, the PEKK composition is thermally stable.
Les résultats obtenus par ATG démontrent que l'aluminium des échantillons 5 et 6 du produit B de l'art antérieur, forme des complexes de nature à générer des vapeurs sous l'effet de la température, qui génèrent des vapeurs suffisantes pour encrasser la lentille de l'équipement de frittage. Le produit C selon l'invention contient des teneurs en aluminium suffisamment basses pour ne pas générer des vapeurs, aucune perte de masse n'étant détectée. La lentille de l'équipement de frittage n'est donc pas encrassée au moment du frittage de la poudre de PEKK selon l'invention.The results obtained by ATG demonstrate that the aluminum of samples 5 and 6 of the product B of the prior art form complexes capable of generating vapors under the effect of temperature, which generate sufficient vapors to foul the lens. sintering equipment. Product C according to the invention contains aluminum contents sufficiently low not to generate vapors, no loss of mass being detected. The lens of the sintering equipment is therefore not fouled at the time of sintering the PEKK powder according to the invention.
La composition de PAEK selon l'invention permet donc de préserver l'équipement de frittage et d'obtenir des objets tridimensionnels frittés avec des propriétés mécaniques satisfaisantes et constantes dans le temps.The composition of PAEK according to the invention thus makes it possible to preserve the sintering equipment and to obtain sintered three-dimensional objects with satisfactory mechanical properties that are constant over time.
Claims (8)
- Poly(aryl-ether-ketone) (PAEK) composition, capable of being used in a process for constructing a three-dimensional object layer-by-layer by electromagnetic radiation-generated sintering, said composition being characterized in that it comprises an aromatic ether content of between 0 and 0.4% by weight, and a weight content of aluminium of less than 1000 ppm, preferably less than 600 ppm and more preferably less than 500 ppm, the content of which is measured in accordance with the description.
- Composition according to Claim 1, characterized in that the composition comprises at least polyether-ketone-ketone (PEKK) which represents more than 60% by weight, preferably more than 70% by weight of the composition, limit included.
- Composition according to Claim 1, characterized in that the composition is a polyether-ketone-ketone (PEKK) composition.
- Composition according to either of Claims 1 and 2, characterized in that the aromatic ether is (1,4-phenoxybenzoyl)benzene.
- Use of a composition according to one of Claims 1 to 4, said composition being in powder form, in a process for constructing an object layer-by-layer by electromagnetic radiation-generated sintering.
- Three-dimensional article obtained by sintering a powder layer-by-layer using electromagnetic radiation, said powder being characterized in that the composition thereof is in accordance with one of Claims 1 to 4.
- Process for synthesizing a poly (aryl-ether-ketone) (PAEK) composition according to one of Claims 1 to 4, said process consisting in:- bringing one or more aromatic acid chlorides and one or more aromatic ethers into contact in the presence of a Lewis acid in a solvent which dissolves water only to a content of less than 0.05% by weight at 25°C at a temperature of between -5°C and +25°C, with stirring;- completing the polymerization at a temperature of between 50°C and 120°C;- bringing the reaction mixture into contact with water, with stirring, in the optional presence of acid;- separating the polyaryl-ether-ketone from the liquid effluents;- washing the polyaryl-ether-ketone in the presence or absence of acid and separating the liquors;- drying the polyaryl-ether-ketone obtained at a temperature 20°C above the glass transition temperature Tg;said process being further characterized in that the step of washing the polyaryl-ether-ketone and of separating the liquors consists in:- carrying out a first washing using a water/alcohol mixture and separating the liquors, the water/alcohol mixture comprising proportions of alcohol of between 95% and 60% by weight, preferably between 95% and 80% by weight;- carrying out at least one other additional washing with water or acid water and separating the liquors.
- Process according to Claim 7, characterized in that the alcohol is chosen from at least one of the following alcohols: methanol, ethanol or isopropanol.
Priority Applications (1)
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EP19205538.2A EP3620482A1 (en) | 2016-05-09 | 2017-05-02 | Poly-(aryl-ether-ketone) (paek) composition with a low content of volatile compounds and use of same in a sintering method |
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FR1654131A FR3050993B1 (en) | 2016-05-09 | 2016-05-09 | LOW-RATE POLY- (ARYL-ETHER-CETONE) (PAEK) COMPOSITION AND ITS USE IN A SINTERING PROCESS |
PCT/FR2017/051043 WO2017194855A1 (en) | 2016-05-09 | 2017-05-02 | Poly-(aryl-ether-ketone) (paek) composition with a low content of volatile compounds and use of same in a sintering method |
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EP19205538.2A Division-Into EP3620482A1 (en) | 2016-05-09 | 2017-05-02 | Poly-(aryl-ether-ketone) (paek) composition with a low content of volatile compounds and use of same in a sintering method |
EP19205538.2A Division EP3620482A1 (en) | 2016-05-09 | 2017-05-02 | Poly-(aryl-ether-ketone) (paek) composition with a low content of volatile compounds and use of same in a sintering method |
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EP3455278A1 EP3455278A1 (en) | 2019-03-20 |
EP3455278B1 true EP3455278B1 (en) | 2019-12-04 |
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EP17725705.2A Active EP3455278B1 (en) | 2016-05-09 | 2017-05-02 | Poly-(aryl-ether-ketone) (paek) composition with a low content of volatile compounds and use of same in a sintering method |
EP19205538.2A Pending EP3620482A1 (en) | 2016-05-09 | 2017-05-02 | Poly-(aryl-ether-ketone) (paek) composition with a low content of volatile compounds and use of same in a sintering method |
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EP19205538.2A Pending EP3620482A1 (en) | 2016-05-09 | 2017-05-02 | Poly-(aryl-ether-ketone) (paek) composition with a low content of volatile compounds and use of same in a sintering method |
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US (1) | US11015071B2 (en) |
EP (2) | EP3455278B1 (en) |
JP (1) | JP6771587B2 (en) |
KR (1) | KR102140390B1 (en) |
CN (1) | CN109153781B (en) |
BR (1) | BR112018071834A2 (en) |
DK (1) | DK3455278T3 (en) |
ES (1) | ES2774738T3 (en) |
FR (1) | FR3050993B1 (en) |
PT (1) | PT3455278T (en) |
WO (1) | WO2017194855A1 (en) |
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US11851526B2 (en) | 2017-06-30 | 2023-12-26 | Solvay Specialty Polymers Usa, Llc | Poly(ether ketone ketone) polymer powder having a low volatiles content |
FR3088647B1 (en) * | 2018-11-15 | 2021-02-26 | Arkema France | REUSABLE POLY (ETHER-KETONE-KETONE) POWDER FOR SINTERING PROCESS |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4716556A (en) | 1981-07-23 | 1987-12-29 | Allied-Signal Inc. | Magnetostrictive acoustic transducer |
US4698393A (en) * | 1983-03-31 | 1987-10-06 | Raychem Corporation | Preparation of poly(arylene ether ketones) |
GB8408082D0 (en) * | 1983-03-31 | 1984-05-10 | Raychem Corp | Preparing poly-(arylene ketones) |
JPS6072923A (en) * | 1983-09-29 | 1985-04-25 | Mitsubishi Chem Ind Ltd | Production of aromatic polyether-ketone |
GB8401411D0 (en) * | 1984-01-19 | 1984-02-22 | Ici Plc | Aromatic polyetherketone |
ES535632A0 (en) * | 1984-03-29 | 1985-11-16 | Raychem Corp | A METHOD OF PRODUCING A POLI (ARILEN-ETER-CETONA) |
US4816556A (en) | 1985-02-22 | 1989-03-28 | E. I. Du Pont De Nemours And Company | Ordered polyetherketones |
US4611033A (en) * | 1985-03-11 | 1986-09-09 | Union Carbide Corporation | Process for stabilizing a poly(aryl ether ketone) |
US4716211A (en) | 1985-03-11 | 1987-12-29 | Amoco Corporation | Slurry process for producing high molecular weight crystalline polyaryletherketones |
US4841013A (en) | 1986-09-18 | 1989-06-20 | Raychem Limited | Preparation of poly(arylene ether ketones) |
US4912181A (en) | 1987-10-20 | 1990-03-27 | Raychem Corporation | Preparation of poly(arylene ether ketones) by sequential oligomerization and polyerization in distinct reaction zones |
FI97291C (en) | 1993-06-17 | 1996-11-25 | Kemira Chemicals Oy | Method for recovering aluminum from a water treatment slurry |
DE102006022442A1 (en) * | 2006-05-13 | 2007-11-15 | Degussa Gmbh | Process for the preparation of polyarylene ether ketone |
US9895842B2 (en) * | 2008-05-20 | 2018-02-20 | Eos Gmbh Electro Optical Systems | Selective sintering of structurally modified polymers |
US8268195B2 (en) * | 2008-09-29 | 2012-09-18 | Air Products And Chemicals, Inc. | Electrically conductive films formed from dispersions comprising polythiophenes and ether containing polymers |
GB0911905D0 (en) | 2009-07-09 | 2009-08-19 | Ketonex Ltd | Method |
DE102011085154A1 (en) | 2011-10-25 | 2013-04-25 | Evonik Industries Ag | Device for preventing deposits on optical components in laser sintering |
EP2788170B1 (en) * | 2011-12-05 | 2021-07-28 | Hexcel Corporation | Method for processing paek and articles manufactured from the same |
CN102702459B (en) * | 2012-06-06 | 2014-02-05 | 吉林大学 | Method for preparing benzene end-capping polyaryletherketone polyme |
FR2993567B1 (en) * | 2012-07-20 | 2015-09-25 | Arkema France | PROCESS FOR THE SYNTHESIS OF POLY-ARYL ETHER-KETONES |
FR3006316B1 (en) | 2013-05-30 | 2015-05-29 | Arkema France | COMPOSITION OF POLYARYLENE-ETHER-KETONE-KETONE POWDERS SUITABLE FOR LASER SINTERING |
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2016
- 2016-05-09 FR FR1654131A patent/FR3050993B1/en not_active Expired - Fee Related
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- 2017-05-02 DK DK17725705.2T patent/DK3455278T3/en active
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- 2017-05-02 JP JP2018558262A patent/JP6771587B2/en active Active
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BR112018071834A2 (en) | 2019-02-19 |
JP6771587B2 (en) | 2020-10-21 |
DK3455278T3 (en) | 2020-03-02 |
WO2017194855A1 (en) | 2017-11-16 |
KR102140390B1 (en) | 2020-07-31 |
FR3050993A1 (en) | 2017-11-10 |
KR20180137001A (en) | 2018-12-26 |
ES2774738T3 (en) | 2020-07-22 |
US20190264045A1 (en) | 2019-08-29 |
PT3455278T (en) | 2020-03-04 |
US20210115277A2 (en) | 2021-04-22 |
CN109153781A (en) | 2019-01-04 |
FR3050993B1 (en) | 2020-01-31 |
JP2019516001A (en) | 2019-06-13 |
US11015071B2 (en) | 2021-05-25 |
CN109153781B (en) | 2021-11-30 |
EP3455278A1 (en) | 2019-03-20 |
EP3620482A1 (en) | 2020-03-11 |
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